US7396593B2 - Single ply tissue products surface treated with a softening agent - Google Patents

Single ply tissue products surface treated with a softening agent Download PDF

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Publication number
US7396593B2
US7396593B2 US10/441,143 US44114303A US7396593B2 US 7396593 B2 US7396593 B2 US 7396593B2 US 44114303 A US44114303 A US 44114303A US 7396593 B2 US7396593 B2 US 7396593B2
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United States
Prior art keywords
tissue
web
sheet
single ply
softening agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related, expires
Application number
US10/441,143
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English (en)
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US20040234804A1 (en
Inventor
Kou-Chang Liu
Tom G. Shannon
Peter J. Allen
Geof Carlow
Mike Goulet
Paul Burden
Greg Aykens
Joe Capizzi
Thomas Hunt
Diane Linskens
Roger Wendler
John Wnek
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Kimberly Clark Worldwide Inc
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Kimberly Clark Worldwide Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Kimberly Clark Worldwide Inc filed Critical Kimberly Clark Worldwide Inc
Priority to US10/441,143 priority Critical patent/US7396593B2/en
Assigned to KIMBERTY-CLARK WORLDWIDE, INC. reassignment KIMBERTY-CLARK WORLDWIDE, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BURDEN, PAUL, ALLEN, PETER J., CAPIZZI, JOE, SHANNON, TOM G., LINSKENS, DIANE, WENDLER, ROGER, GOULET, MIKE, LIU, KOU-CHANG, AYKENS, GREG, CARLOW, GEOF, HUNT, THOMAS, WNEK, JOHN
Priority to PCT/US2004/006913 priority patent/WO2004104298A2/fr
Priority to EP20080005963 priority patent/EP1950346A3/fr
Priority to BRPI0410008 priority patent/BRPI0410008A/pt
Priority to AU2004242060A priority patent/AU2004242060B2/en
Priority to CA2524685A priority patent/CA2524685C/fr
Priority to EP20040717506 priority patent/EP1627108B1/fr
Priority to MXPA05011736A priority patent/MXPA05011736A/es
Priority to KR1020057020915A priority patent/KR20060008978A/ko
Publication of US20040234804A1 publication Critical patent/US20040234804A1/en
Priority to US12/165,152 priority patent/US7897015B2/en
Publication of US7396593B2 publication Critical patent/US7396593B2/en
Application granted granted Critical
Assigned to KIMBERLY-CLARK WORLDWIDE, INC. reassignment KIMBERLY-CLARK WORLDWIDE, INC. NAME CHANGE Assignors: KIMBERLY-CLARK WORLDWIDE, INC.
Adjusted expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • D21H21/24—Surfactants
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B15/00—Details of spraying plant or spraying apparatus not otherwise provided for; Accessories
    • B05B15/50—Arrangements for cleaning; Arrangements for preventing deposits, drying-out or blockage; Arrangements for detecting improper discharge caused by the presence of foreign matter
    • B05B15/52—Arrangements for cleaning; Arrangements for preventing deposits, drying-out or blockage; Arrangements for detecting improper discharge caused by the presence of foreign matter for removal of clogging particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B15/00—Details of spraying plant or spraying apparatus not otherwise provided for; Accessories
    • B05B15/50—Arrangements for cleaning; Arrangements for preventing deposits, drying-out or blockage; Arrangements for detecting improper discharge caused by the presence of foreign matter
    • B05B15/55—Arrangements for cleaning; Arrangements for preventing deposits, drying-out or blockage; Arrangements for detecting improper discharge caused by the presence of foreign matter using cleaning fluids
    • B05B15/555—Arrangements for cleaning; Arrangements for preventing deposits, drying-out or blockage; Arrangements for detecting improper discharge caused by the presence of foreign matter using cleaning fluids discharged by cleaning nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
    • B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
    • B05C5/027—Coating heads with several outlets, e.g. aligned transversally to the moving direction of a web to be coated
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/50—Spraying or projecting
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/002—Tissue paper; Absorbent paper
    • D21H27/008—Tissue paper; Absorbent paper characterised by inhomogeneous distribution or incomplete coverage of properties, e.g. obtained by using materials of chemical compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/02—Spray pistols; Apparatus for discharge
    • B05B7/08—Spray pistols; Apparatus for discharge with separate outlet orifices, e.g. to form parallel jets, i.e. the axis of the jets being parallel, to form intersecting jets, i.e. the axis of the jets converging but not necessarily intersecting at a point
    • B05B7/0807—Spray pistols; Apparatus for discharge with separate outlet orifices, e.g. to form parallel jets, i.e. the axis of the jets being parallel, to form intersecting jets, i.e. the axis of the jets converging but not necessarily intersecting at a point to form intersecting jets
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24446—Wrinkled, creased, crinkled or creped
    • Y10T428/24455—Paper
    • Y10T428/24463—Plural paper components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31975—Of cellulosic next to another carbohydrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31975—Of cellulosic next to another carbohydrate
    • Y10T428/31978—Cellulosic next to another cellulosic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31975—Of cellulosic next to another carbohydrate
    • Y10T428/31978—Cellulosic next to another cellulosic
    • Y10T428/31986—Regenerated or modified
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31993—Of paper

Definitions

  • tissue products such as facial tissue, bath tissue, paper towels, dinner napkins and the like
  • product properties are imparted to the final product through the use of chemical additives.
  • one common attribute imparted to tissue sheets through the use of chemical additives is softness, particularly topical or surface softness.
  • tissue products are treated with polysiloxanes in order to increase the softness of the tissue.
  • tissue products may be treated with other beneficial agents as well.
  • other desirable agents may be added to a tissue in order to provide a benefit to the user.
  • vitamins, plant extracts, medications, antimicrobial compounds, and the like may also be added to the web in order to transfer the desired agent to the consumer upon use.
  • a similar method to rotogravure printing is also known in the art.
  • the polysiloxane emulsion is applied to a heated transfer roll to remove some of the solvent (water).
  • the concentrated silicone emulsion is then transferred from the heated transfer roll to the surface of the tissue. While this process may provide some benefits from the drying time required by the conventional rotogravure process it still requires the use of dilute solutions emulsions containing surfactants and therefore does not address the issues of additional chemicals, increased wet out times and process complexity.
  • both the rotogravure and transfer roll process require the tissue to be subjected to Z-directional compressive forces which in combination with the water, surfactants and other diluents present tend to reduce the bulk of the finished product.
  • these Z-directional compressive forces tend to drive the chemicals into the bulk of the tissue whereby the chemical can penetrate a significant distance into the Z-direction of the sheet.
  • the softening agents applied in this manner are intended to improve the surface feel, the chemical that penetrates in the Z-direction of the sheet is not effective and hence more chemistry is required than if it were all retained on the tissue surface.
  • Spray atomization is the process of combining a chemical with a pressurized gas to form small droplets that are directed onto a substrate, such as paper.
  • a substrate such as paper.
  • One problem posed with atomization processes is that manufacturers often find it difficult to control the amount of chemical that is applied to a paper ply.
  • a frequent problem with spray atomization techniques is that a large amount of over-spray is generated, which undesirably builds upon machinery as well as the surfaces of equipment and products in the vicinity of the spray atomizer.
  • over-spray wastes the chemical being applied, and comprises a generally inefficient method of applying additives to a tissue web.
  • a softening agent such as a polysiloxane
  • the present invention is directed to an improved process for applying compositions to tissue products, such as facial and bath tissues, paper towels and other wipers.
  • tissue products such as facial and bath tissues, paper towels and other wipers.
  • the present invention is also directed to improved tissue sheets made from the process.
  • the present invention is directed to a single ply tissue web containing cellulosic fibers.
  • the cellulosic fibers may be hardwood fibers, softwood fibers, or mixtures thereof.
  • the tissue web can have a basis weight of from about 5 gsm to about 200 gsm, such as from about 5 gsm to about 80 gsm.
  • the tissue web can also have a bulk of greater than about 2 cc/g and in specific embodiments greater than about 7 cc/g.
  • the tissue web includes a first side, a center, and a second and opposite side.
  • a softening agent is present at the first side and at the second side of the tissue web.
  • the softening agent is distributed non-uniformly across the thickness of the tissue web so as to form a gradient in the Z-direction of the web.
  • the softening agent may be present at the first and second sides of the web in an amount that is at least 15% (atomic amount) greater than the amount of softening agent contained at the center of the web.
  • the softening agent may be present at the first and second sides of the web in an amount that is at least 25% greater, 50% greater, or even 70% greater than the amount of softening agent contained at the center of the single ply web.
  • the softening agent is a polysiloxane.
  • the polysiloxane may be topically applied to each side of the tissue web, may cover from about 0.5% to about 80% of the surface area of each side, and may be added to the tissue web in an amount from about 0.05% to about 5% by weight of dry fibers.
  • the polysiloxane may be combined with a skin beneficial agent, such as aloe vera, vitamin E, petrolatum, and mixtures thereof.
  • the softening agent such as polysiloxane
  • a tissue web may be constructed containing virtually no surfactants.
  • the tissue web may have a total surfactant content of less than about 0.08% by weight, more specifically about less than 0.05% by weight and still more specifically less than about 0.025% by weight of the dry fibers. Even without the presence of surfactants, the tissue web can have a Wet Out Time of less than about 10 seconds, such as less than about 8 seconds.
  • the softening agent may be applied topically to each side of the tissue web using, for instance, an extruder such as a meltblown die. In this manner, the softening agent may form a random continuous network on each side of the tissue web. The softening agent may form, for instance, continuous filaments across the surface of each side of the web.
  • the present invention is also directed to a cleaning device for cleaning a chemical additive applicator, such as a meltblown die, that is intended to apply chemical additives to tissue webs.
  • the apparatus of the present invention includes a conveying device for supporting and moving a web.
  • a chemical additive applicator is positioned in relation to the conveying device so as to apply a chemical additive to the moving web.
  • the chemical additive applicator comprises a row of orifices for emitting the chemical additive.
  • the apparatus further includes a cleaning device for periodically removing debris from the row of orifices of the chemical additive applicator.
  • the cleaning device for instance, comprises a brush that traverses across the orifices.
  • the brush may be mounted on a track for traversing across the chemical additive applicator. In one embodiment, the brush may also rotate as it traverses across the applicator. In an alternative embodiment, the brush may have a width that is substantially the same width as the chemical additive applicator and may move back and forth across the applicator for cleaning the orifices. In this embodiment, the brush may include a continuous row of bristles or may be comprised of separate segments. Further, instead of moving back and forth, the brush may also be configured to rotate about an axis for cleaning the die head. In this embodiment, the brush may transition between a cleaning position and a disengagement position.
  • the above described brush may be used in combination with a plurality of fluid (liquid or gas) jet nozzles and/or a vacuum device.
  • the fluid nozzles may be positioned adjacent to the row of orifices on the chemical additive applicator and may be configured to emit a fluid against the orifices for cleaning them periodically.
  • a vacuum device may include at least one suction chamber also mounted adjacent to the orifices for removing debris and other contaminates.
  • the fluid nozzles and/or the vacuum nozzles may be mounted directly on the brush for assisting the brush in cleaning the chemical additive applicator.
  • FIG. 1 is a schematic drawing showing application of a viscous composition through a meltblown die tip onto a paper web in accordance with the present invention.
  • FIG. 2 is a side view of one embodiment of a meltblown die that may be used in accordance with the present invention
  • FIG. 3 is a bottom view of a portion of the meltblown die illustrated in FIG. 2 showing, in this embodiment, a row of orifices through which compositions are extruded;
  • FIG. 4 is a plan view of one embodiment of a paper web made in accordance with the present invention.
  • FIG. 5 illustrates one embodiment of the process of the present invention
  • FIG. 6 is a top view of air intakes on a vacuum box which may be used in accordance with the present invention.
  • FIG. 7 is a perspective view of one embodiment of a cleaning device for cleaning a meltblown die in accordance with the present invention.
  • FIG. 8 is another perspective view of the cleaning device shown in FIG. 7 including a shield member or housing covering a portion of the meltblown die;
  • FIG. 9 is a perspective view of the cleaning device shown in FIG. 7 further including a scraping device for cleaning a brush that traverses across the meltblown die;
  • FIG. 10 is a perspective view of another embodiment of a cleaning device that may be used in accordance with the present invention.
  • FIG. 11 is a perspective view of still another embodiment of a cleaning device that may be used in accordance with the present invention.
  • FIG. 12 is a perspective view of one embodiment of a plurality of fluid nozzles positioned adjacent to a row of orifices on a meltblown die for periodically cleaning the die tip;
  • FIG. 13 is a perspective view of an alternative embodiment of a fluid or vacuum nozzle that may be used to clean the meltblown die
  • FIG. 14 is a perspective view of another embodiment of a meltblown die shown in combination with a cleaning device for the orifices located on the meltblown die;
  • FIG. 15 is a perspective view of still another embodiment of a cleaning device for use in the present invention.
  • the present invention is directed to applying viscous chemical compositions on to a tissue sheet, such as a single ply tissue web using, for instance, a meltblown die. It has been found that when compared with the rotogravure printing process and the spray atomization process, the meltblown process is more efficient.
  • the process of the present invention for applying compositions to tissue webs may be simpler and less complex.
  • the process of the present invention also provides more flexibility with respect to operation parameters. For instance, it has been found that the process of the present invention provides better controls over flow rates and add on levels of the compositions being applied to the tissue webs. In some applications, the process of the present invention may also allow the compositions to be applied to the tissue webs at higher speeds in comparison to many rotogravure printing processes.
  • the process of the present invention may provide greater control over application rates and may apply compositions to tissue webs more uniformly.
  • the process of the present invention also may better prevent against over application of the composition and may provide better controls over placement of the composition onto the web.
  • additives may be applied to tissue webs without first combining the additives with anything which could dilute the additives, e.g., solvents, surfactants, preservatives, antifoamers, and the like.
  • Such diluents required for application via conventional technologies allows, among other problems, the additive to penetrate the Z-direction of the sheet.
  • For surface treatment it is desirable to keep material from penetrating the bulk of the tissue sheet.
  • For application of lotions containing oils and waxes it is known to apply waxes that are solids at room temperature by melting the lotion. These lotions have a relatively low melting point, generally less than 70° C. and show Newtonian behavior where the viscosity drops quickly with increasing temperature. Hence, in the heated state they can be applied via conventional technologies. During application to the sheet rapid cooling and crystallization can keep more lotion on the surface of the tissue sheet to aid transfer to the user's skin.
  • MW molecular weight
  • polysiloxanes do not demonstrate good Newtonian behavior and thus their viscosity does not change significantly with increasing temperature.
  • high molecular weight or high viscosity polysiloxanes are incapable of being added using conventional technologies without the presence of a diluent such as an emulsifier and water mixture.
  • the process of the present invention may be more economical and less complex than many conventional application systems and further allows for the application of high viscosity polysiloxanes without the need for additional diluents.
  • a composition containing a chemical additive in accordance with the present invention may be applied to a tissue sheet in the form of fibers, such as, for instance, in the form of continuous fibers.
  • a tissue sheet in the form of fibers such as, for instance, in the form of continuous fibers.
  • compositions applied in accordance with the present invention will fiberize when extruded through the meltblown die tip.
  • the ability to fiberize the compositions provides various advantages. For example, when formed into fibers, the composition is easily captured by the sheet. The fibers may also be placed on the sheet in specific locations. Further, when desired, the fibers will not penetrate through the entire thickness of the sheet, but instead, will remain on the surface of the sheet, where the chemical additives are intended to provide benefits to the consumer. For example, more than about 70% of the composition applied to the sheet in the form of fibers may remain on the surface of the treated sheet.
  • the fibers can take various forms.
  • the fibers appear randomly deposited over the surface of the tissue sheet in an intersecting network.
  • small pools of the chemical additive may form on the surface of the sheet. Strands or fibers of the chemical additive may then extend from the pools and possibly intersect with other pools that are present.
  • the fibers When deposited on the paper web, the fibers may be very sinuous appearing as thread-like filaments containing multiple curvatures.
  • the present invention is directed to a single ply tissue product that has been treated on both sides with a chemical additive as described above.
  • a chemical additive such as a softening agent
  • single ply tissue products can be produced that have improved softness at a lower level of additive and higher bulk. Improved softness at lower levels of additive arises from reduced bulk penetration of the softening agent.
  • single ply tissue products can be produced having a chemical additive content that is at a minimum at the center of the sheet and extends to a maximum at both exterior surfaces.
  • chemical additives can be applied to a single ply web in a manner that forms a Z-directional gradient.
  • the Z-directional gradient may be determined by X-ray photoelectron spectroscopy (XPS) as described hereinafter. Surface additive levels are reported as atomic concentration as determined by the spectrometer. The atomic concentration is measured to a depth of about 100 nanometers and is indicative of the additive content at the surface of the tissue web.
  • Z-directional gradients are defined as a percent difference in atomic concentration between the exterior surfaces of the tissue web and the middle of the web.
  • a soft, single ply tissue product may be formed in which a chemical additive, such as a softening agent, is present on both exterior surfaces of the product, but is non-uniformly distributed throughout the thickness of the product.
  • tissue products can be made according to the present invention having a percent Z-directional additive gradient between the exterior surfaces of the product and the center of the product in an amount of about 15% or greater, such as in an amount of about 25% or greater.
  • the Z-directional gradient between the exterior surfaces of the single ply web and the center of the web may be greater than about 50%, and even greater than about 70%.
  • Another advantage of the present invention is that for some applications, a lesser amount of the chemical additive may be applied to the web than what was necessary in typical rotogravure processes while still obtaining an equivalent or better result.
  • the chemical additive may be applied in a relatively viscous form without having to be formed into an emulsion or a solution and because the chemical additive may be applied as fibers uniformly over the surface of a web, it is believed that the same or better results may be obtained without having to apply as much of the chemical additive as was utilized in many prior art processes.
  • a softener may be applied to a web in a lesser amount while still obtaining the same softening effect in comparison to rotogravure processes and spray processes.
  • the product also may have better wettability, as may be measured by wet-out time. Further, since less of the chemical additive is needed, additional cost savings are realized.
  • a composition containing a chemical additive is applied to a tissue web.
  • the chemical additive may be, for instance, a softener.
  • more than one chemical additive may be combined and applied to a web.
  • a softener such as a polysiloxane softener may be combined with one or more chemical agents which may provide a desired benefit to the consumer and then the combination may be applied to a tissue web according to the present invention.
  • tissue webs in accordance with the present invention include, without limitation, anti-acne actives, antimicrobial actives, antifungal actives, antiseptic actives, antioxidants, cosmetic astringents, drug astringents, deodorants, emollients, external analgesics, film formers, fragrances, humectants, natural moisturizing agents and other skin moisturizing ingredients known in the art such as lanolin, skin conditioning agents, skin exfoliating agents, skin protectants, and sunscreens. More specifically, vitamin E and aloe vera extracts are examples of beneficial agents which may be applied to a surface of a web according to the present inventive process.
  • the above chemical additives may be applied alone or in combination with other additives in accordance with the present invention.
  • the desired polysiloxane softeners may be mixed with the desired beneficial agents and applied together as a single composition.
  • the softeners and beneficial agents may be applied separately, creating layers of additives on the surface of the tissue web.
  • the process is directed to applying one or more softeners and one or more beneficial agents to a tissue web.
  • the softener may be, for instance, a polysiloxane that makes a tissue product feel softer to the skin of a user.
  • Suitable polysiloxanes that may be used in the present invention include amine, aldehyde, carboxylic acid, hydroxyl, alkoxyl, polyether, polyethylene oxide, and polypropylene oxide derivatized silicones, such as aminopolydialkylsiloxanes.
  • the two alkyl radicals may be methyl groups, ethyl groups, and/or a straight branched or cyclic carbon chain containing from about 3 to about 8 carbon atoms.
  • Some commercially available examples of polysiloxanes include WETSOFT CTW, AF-21, AF-23 and EXP-2025G of Kelmar Industries, Y-14128, Y-14344, Y-14461 and FTS-226 of the Crompton Corporation, and Dow Corning 8620, Dow Corning 2-8182, Dow Corning HMW2220 and Dow Corning 2-8194 of the Dow Corning Corporation.
  • Polysiloxanes encompass a very broad class of compounds. They are characterized in having a backbone structure:
  • R′ and R′′ can be a broad range of organo and non-organo groups including mixtures of such groups and where n is an integer greater than 2.
  • These polysiloxanes may be linear, branched or cyclic. They include a wide variety of polysiloxane copolymers containing various compositions of functional groups, hence, R′ and R′′ actually may represent many different types of groups within the same polymer molecule.
  • the organo or non-organo groups may be capable of reacting with cellulose to covalently, ionically or hydrogen bond the polysiloxane to the cellulose.
  • These functional groups may also be capable of reacting with themselves to form crosslinked matrixes with the cellulose.
  • the polysiloxane component is referred to as a polydialkylsiloxane component.
  • the scope of the invention should not be construed as limited by a particular polysiloxane structure so long as that polysiloxane structure delivers the aforementioned product or process benefits
  • the softness benefits that polysiloxanes deliver to cellulose containing products is believed to be, in part, related to the molecular weight of the polysiloxane.
  • Viscosity is often used as an indication of molecular weight of the polysiloxane as exact number or weight average molecular weights are often difficult to determine.
  • the viscosity of the polysiloxanes of the present invention is greater than about 50 centipoise, more preferably greater than 100 centipoise and most preferably greater than 200 centipoise. In one embodiment the viscosity of the polysiloxane is greater than about 1500 centipoise.
  • Viscosity refers to the viscosity of the neat polysiloxane itself and not to the viscosity of an emulsion if so delivered. It should also be understood that the polysiloxanes of the current invention may be delivered as solutions containing diluents. Such diluents may lower the viscosity of the solution below the limitations set above, however, the efficacious part of the polysiloxane should conform to the viscosity ranges given above.
  • diluents include but is not limited to oligomeric and cyclo-oligomeric polysiloxanes such as octamethylcyclotetrasiloxane, octamethyltrisiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane and the like including mixtures of said compounds.
  • a specific class of polysiloxanes suitable for the invention has the general formula:
  • R 1 -R 8 moieties can be independently any organofunctional group including C 1 or higher alkyl groups, ethers, polyethers, polyesters, amines, imines, amides, or other functional groups including the alkyl and alkenyl analogues of such groups and y is an integer >1.
  • the R 1 -R 8 moieties are independently any C 1 or higher alkyl group including mixtures of said alkyl groups, such materials referred to as polydialkylsiloxanes.
  • Exemplary polysiloxanes are the DC-200 fluid series, manufactured and sold by Dow Corning, Inc. As softness is believed to be at least in part related to the molecular weight of the polysiloxane, especially preferred compounds are high MW linear polydialkylsiloxanes such as DC-HMW2220 sold by Dow Corning, Inc.
  • x and y are integers >0.
  • the mole ratio of x to (x+y) can be from about 0.005 percent to about 25 percent.
  • the R 1 -R 9 moieties can be independently any organofunctional group including C 1 or higher alkyl groups, ethers, polyethers, polyesters, amines, imines, amides, or other functional groups including the alkyl and alkenyl analogues of such groups.
  • the R 10 moiety is an amino functional moiety including but not limited to primary amine, secondary amine, tertiary amines, quaternary amines, unsubstituted amides and mixtures thereof.
  • An exemplary R 10 moiety contains one amine group per constituent or two or more amine groups per substituent, separated by a linear or branched alkyl chain of C 1 or greater.
  • R 7 and R 8 are alkyl groups such as C 1 -C 8 alkyl groups the polysiloxanes are hereinafter referred to as aminofunctional polysiloxanes, more specifically amino functional polydialkylsiloxanes.
  • Exemplary materials include DC 2-8220 and DC 2-8182 commercially available from Dow Corning, Inc., Midland, Mich. and Y-14344 available from Crompton, Corp., Greenwich, Conn.
  • polysiloxanes Another exemplary class of functionalized polysiloxanes is the polyether polysiloxanes. Such polysiloxanes are again widely taught in the art and are usually incorporated wholly or in part with other functional polysiloxanes as a means of improving hydrophilicity of the silicone treated product. Such polysiloxanes generally have the following structure:
  • x and z are integers >0, y is an integer 0.
  • the mole ratio of x to (x+y+z) can be from about 0.05 percent to about 95 percent.
  • the ratio of y to (x+y+z) can be from about 0 percent to about 25%.
  • the R 0 -R 9 moieties can be independently any organofunctional group including C 1 or higher alkyl groups, ethers, polyethers, polyesters, amines, imines, amides, or other functional groups including the alkyl and alkenyl analogues of such groups.
  • the R 10 moiety is an amino functional moiety including but not limited to primary amine, secondary amine, tertiary amines, quaternary amines, unsubstituted amides and mixtures thereof.
  • An exemplary R 10 moiety contains one amine group per constituent or two or more amine groups per substituent, separated by a linear or branched alkyl chain of C 1 or greater.
  • R 11 is a polyether functional group having the generic formula: R 12 —(R 13 —O) a —(R 14 O) b —R 15 , wherein R 12 , R 13 , and R 14 are independently C 1-4 alkyl groups, linear or branched; R 15 can be H or a C 1-30 alkyl group; and, “a” and “b” are integers of from about 1 to about 100, more specifically from about 5 to about 30.
  • Exemplary aminofunctional polyetherpolysiloxanes and aminofunctional polyetherpolydialkylsiloxanes are the Wetsoft CTW family manufactured and sold by Wacker, Inc., Adrian, Mich.
  • Other exemplary polysiloxanes can be found in U.S. Pat. No. 6,432,270 by Liu, et. al, and incorporated by reference herein.
  • a polysiloxane softener of the following general chemical structure may be utilized in the process of the present invention:
  • A is hydrogen; hydroxyl; or straight chain, branched or cyclic, unsubstituted or substituted, C 1 -C 8 alkyl or alkoxy radicals;
  • R 1 -R 8 are independently, a straight chain, branched or cyclic, unsubstituted or substituted, C 1 -C 6 alkyl radical;
  • m is from 20 to 100,000
  • p is from 1 to 5,000
  • q is from 0 to 5,000
  • D is the following: —R 15 —(OC 2 H 5 ) x —(OC 3 H 7 ) y —O—R 16
  • a polysiloxane having the following general structure may also be utilized in the present invention:
  • X is hydrogen; hydroxyl; or straight chain, branched or cyclic, unsubstituted or substituted, C 1 -C 8 alkyl or C 1 -C 8 alkoxyl radical;
  • Y is the following:
  • Z is hydrogen or a straight chain, branched or cyclic, unsubstituted or substituted, C 1 -C 24 alkyl radical.
  • polysiloxanes were typically combined with water, preservatives, antifoamers, and surfactants, such as nonionic ethoxylated alcohols, to form stable and microbial-free emulsions and applied to tissue webs. Since the process of the present invention may accommodate higher viscosities, however, the polysiloxanes may be added directly to a tissue web or to another paper product without having to be combined with water, a surfactant or any other agent. For example, neat compositions, such as a neat polysiloxane composition or a neat beneficial agent may be applied to the surface of the web separately in any desired order in accordance with the present invention.
  • a mixed composition including only a polysiloxane and a beneficial agent may be prepared and applied together in a single layer. Since the polysiloxane and the beneficial agents may be applied to a web without having to be combined with any other ingredients, the process of the present invention may be more economical and less complex than many prior processes. Further, as described above, it has also been discovered that lesser amounts of the chemical additives may be applied to the web while still obtaining the same or better results, which may provide additional cost savings.
  • the present invention is directed to a tissue product, such as a single ply tissue web, that contains no appreciable amounts of surfactants.
  • the present invention is directed to a single ply tissue product having a polydialkylsiloxane content of greater than about 0.1% while also having a surfactant content of less than about 10% by weight of the amount of polydialkylsiloxane present in the web, in another embodiment less than about 5% by weight the amount of polydialkylsiloxane present in the web and in still another embodiment less than about 2% by weight of the amount of polysiloxane present in the web.
  • the tissue web may have a polydialkylsiloxane content of from 0.3% and can have a surfactant concentration of less than about 0.03%, such as less than about 0.015%, or such as less than about 0.006%.
  • polydialkylsiloxane it is meant the portion of the polysiloxane comprising dialkylsiloxane monomer units of the formula:
  • R′ and R′′ are independently C 1 -C 30 groups including mixtures of said alkyl groups.
  • R′ and R′′ are CH 3 and the polysiloxane component is referred to as polydimethylsiloxane.
  • the polydialkylsiloxane content can be measured by converting the dialkylsiloxane component to diflourodialkylsilane with BF 3 and measuring the level of the diflourodialkylsilane with gas chromatography as hereinafter described.
  • a surfactant generally refers to a composition that reduces the surface tension of liquids, or reduces interfacial tension between two liquids or a liquid and a solid.
  • the presence of surfactants in tissue products is not necessarily unfavorable.
  • the incorporation of surfactants, particularly ionic surfactants, into tissue sheets may provide various advantages.
  • surfactants may be used for their debonding properties.
  • many commercially available debonders act as cationic surfactants.
  • non-ionic emulsifiers or surfactants generally do not assist in improving the handfeel of the tissue product. They are also not substantive in the wet end of the process and therefore their presence indicates application via some sort of post treatment process after web formation.
  • non-ionic surfactants include, but are not limited to polyoxyethylene alkylamines, trialkylamine oxides, triethanol amine fatty acid esters and partial fatty acid esters, polyoxyethylene alkyl ethers such as those obtained by ethoxylation of long chain alcohols, polyoxyethylene alkenyl ethers, alkylphenyl ethoxylates, polyoxyethylene polystyriphenyl ethers, polypropylene glycol fatty acid esters and alkyl ethers, polyethylene glycol fatty acid esters and alkyl ethers, polyhydric alcohol fatty acid partial esters and alkyl ethers, glycerin fatty acid esters, polyglycerin fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid partial esters and alkyl ethers, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene fatty acid esters and alkyl ethers, polyg
  • Non-ionic surfactant concentration in the tissue can be determined using a variety of methods or appropriate commercially available test kits as described hereinafter.
  • An example of one such kit is the Dr. Lange non-ionic test solutions available from Dr. Bruno Lange, GmbH, Dusseldorf, Germany.
  • Levels of non-ionic surfactant are determined by extraction of the surfactant from the tissue web with water and measuring the absorbency of the filtrate at a wavelength of 620 nm after treatment with the components of the kit. The absorption at 620 nm is directly related to the concentration of non-ionic surfactant in the tissue web.
  • the products of the present invention have filtrates having an absorbency of less than about 0.16, more specifically less than about 0.13 and still more specifically less than about 0.10 or an absorbency to polydialkylsiloxane content ratio of less than about 0.75, more specifically less than about 0.65 and still more specifically less than about 0.50.
  • ionic surfactants include primary, secondary and tertiary amine salts of the corresponding alkyl amines, alkyltrimethyl ammonium salts, dialkyldimethyl benzonium salts, dialkyldimethyl ammonium salts, trialkylmethyl ammonium salts, tetra alkyl ammonium salts, polyethylenepolyamine fatty acid amide salts, fatty acid salts, alkylbenzenesulfonates, dialkylsulfosuccinates, alkylsulfonates, N-acyl-N-methyltaurate, alkylsulfates, sulfonated fats and oils, polyoxyethylene alkylether sulfonates, polyoxyethylene styrenated phenyl ether sulfonates, alkyphosphates, polyoxyethylene alkyl phenyl ether phosphates, N,N-dimethyl-N-alkyl-N-carboxymethylam
  • polysiloxanes and other additives were also used sparingly in some applications due to their hydrophobicity.
  • problems have been experienced in applying polysiloxane softeners to bath tissues due to the adverse impact upon the wettability of the tissue.
  • hydrophobic compositions may be applied to tissue webs for improving the properties of the webs while maintaining acceptable wettability properties.
  • a hydrophobic composition may be applied in a discrete, discontinuous, or heterogeneous manner to a tissue web in order to maintain a proper balance between improving the properties of the web through the use of the composition and maintaining acceptable absorbency and wettability characteristics.
  • a composition may be applied to a surface of the web in such a fashion so as to apply varying amounts of the composition to the web at different surface locations.
  • the web may have composition in the form of fibers covering sections of the web, and no composition at other areas of the web, such as between the individual fibers which are extruded onto the web surface.
  • the composition can cover the web in a heterogeneous fashion, with composition coverage varying across the surface of the web.
  • a tissue web 21 moves from the right to the left and is comprised of a first side 45 that faces upwards and a second side 46 that faces downward.
  • the tissue web 21 receives a viscous composition stream 29 upon its first side 45 .
  • the composition stream 29 is applied to the web 21 after the web has been formed.
  • the composition may be applied to the web, for instance, after the web has been formed and prior to being wound.
  • the composition may be applied in a post treatment process in a rewinder system.
  • the chemical composition may be applied prior to the drying section of the tissue process where the tissue web has a consistency of from about 10% to about 60%.
  • the chemical composition may be applied in the drying section of the tissue web where the tissue web has a consistency of about 30% to about 100%.
  • the chemical composition may be applied to the tissue web after being dried but before being wound where the tissue web has a consistency of about 90% to about 100%.
  • the tissue web may have a consistency of from about 90% to about 100%.
  • the web 21 may be calendered, using calender rolls 25 and 26 subsequent to application of the composition.
  • the web may be calendered and thereafter the composition may be applied to the web.
  • the calender rolls may provide a smooth surface for making the product feel softer to a consumer.
  • a single composition containing one or more polysiloxane softeners optionally combined with one or more beneficial agents is extruded to form a composition stream 29 that is directed onto the web 21 .
  • the extruder includes a meltblown die 27 .
  • a meltblown die is an extruder that includes a plurality of fine, usually circular, square or rectangular die capillaries or nozzles that may be used to form fibers.
  • a meltblown die may include converging high velocity gas (e.g. air) streams which may be used to attenuate the fibers exiting the nozzles.
  • a meltblown die is disclosed, for instance, in U.S. Pat. No. 3,849,241 to Butin, et al which is incorporated herein by reference.
  • meltblown die 27 extrudes the viscous composition stream 29 from die tip 28 .
  • the meltblown die may be placed in association with air curtain 30 a - b .
  • the air curtain 30 a - b may completely surround the extruded composition stream 29 , while in other applications the air curtain 30 a - b may only partially surround the composition stream 29 .
  • the air curtain may facilitate application of the composition to the tissue web, may assist in forming fibers from the composition being extruded and/or may attenuate any fibers that are being formed.
  • the air curtain may be at ambient temperature or may be heated.
  • An exhaust fan 31 is provided to improve air flow and to employ a pneumatic force to pull the composition stream 29 down on to the first side 45 of the tissue web 21 .
  • the exhaust fan 31 is shown contained within a vacuum box. It should be understood, however, that the exhaust fan may be located downstream from the vacuum box if desired.
  • the exhaust fan 31 serves to remove from the immediate vicinity airborne particles or other debris through an exhaust duct 32 .
  • the exhaust fan 31 operates by pulling air using the rotating propeller 33 shown in dotted phantom in FIG. 1 .
  • FIG. 2 a more detailed view of the meltblown die 27 is shown in which air intake 34 a - b brings air into the meltblown die 27 .
  • Air travels into air duct 35 and air duct 36 , respectively, from air intake 34 a and 34 b .
  • the air proceeds along air pathway 37 and air pathway 38 , respectively, to a point near the center of die tip 28 at which the air is combined with a viscous composition entering the meltblown die from a port 40 .
  • the composition contains the desired polysiloxane softeners and beneficial agents that emerges from a reservoir 39 to die tip 28 . Then, the composition travels downward as viscous composition stream 29 , shielded by air curtain 30 a - b.
  • FIG. 3 shows a bottom view of the meltblown die 27 as it would appear looking upwards from the tissue web 21 (as shown in FIG. 1 ) along the path of the composition stream 29 to the point at which it emerges from die tip 28 .
  • the meltblown die 27 is comprised of orifices 42 (several of which are shown in FIG. 3 ), and such orifices 42 may be provided in a single row as shown in FIG. 3 .
  • a combination of channels and orifices 42 could be used.
  • multiple rows of openings could be provided, and there is no limit to the different geometrical arrangement and patterns that could be provided to the meltblown die 27 for extruding a composition stream 29 within the scope of the invention.
  • a pressurized tank (not shown) transfers a gas, such as air, to the meltblown die 27 for forcing the composition through the die tip.
  • a pump such as a gear pump, may use hydraulic pressure to push the composition through the meltblown die 27 .
  • the composition is forced through the meltblown die 27 and extruded through, for instance, holes or orifices spaced along the length of the die tip.
  • the size of the orifices and the amount of the orifices located on the meltblown die tip may vary depending upon the particular application.
  • the orifices may have a diameter from about 5 mils to about 25 mils, and particularly from about 5 mils to about 10 mils.
  • the orifices may be spaced along the die tip in an amount from about 3 orifices per inch to about 50 orifices per inch, and particularly from about 3 orifices per inch to about 20 orifices per inch.
  • Two streams of pressurized air converge on either side of the composition stream 29 after it exits the meltblown die 27 .
  • the resulting air pattern disrupts the laminar flow of the composition stream 29 and attenuates the fibers being formed as they are directed onto the surface of the web.
  • Different sized orifices or nozzles will produce fibers having a different diameter.
  • the fibers that may be formed according to the present invention include discontinuous fibers and continuous fibers.
  • the fibers may have various diameters depending upon the particular application. For instance, the diameter of the fibers may vary from about 5 microns to about 300 microns, such as from about 5 microns to about 200 microns or to about 100 microns.
  • continuous fibers are formed having a diameter of about 25 microns.
  • the composition may be applied to both surfaces 45 , 46 of a web 21 in a post treatment process.
  • the web 21 may be unwound from a roll 22 .
  • the web is calendered using calender rolls 25 and 26 prior to application of the composition.
  • the web surface 45 which will be accepting the composition may be cleaned of loose fibers and lint by sheet cleaner 1 prior to application of the composition.
  • compositions which may be applied to the surface of the web according to the present invention tend to be not only viscous, but also somewhat tacky prior to application on the web.
  • one embodiment of the present invention contemplates application of a very high viscosity neat polysiloxane composition, which is also quite tacky when not applied to the tissue web.
  • tissue webs tend to carry a great deal of particulate matter, with a lot of lint and loose fibers associated with the base sheet.
  • the combination of the tacky composition and the particulates associated with the tissue web at the meltblown die may cause the die tips to become clogged and block the composition flow to the web.
  • the process and system of the present invention may prevent contact between particulate matter associated with the tissue web and the die tips of the meltblown die and may therefore avoid the expense of down time of production due to clogged die tips.
  • sheet cleaner 1 may be, for example, a vacuum system which may remove lint and loose fibers from the surface 45 of web 21 prior to application of the composition 29 .
  • a composition comprising the polysiloxane softener and, in one embodiment, the beneficial agent may be applied to the surface 45 of the web.
  • the composition may be applied by use of a meltblown die 27 which may extrude the composition stream and direct it to the surface of web 21 .
  • the different chemical additives may be applied to the surface of the web in separate steps, such as, for instance, with a series of meltblown dies, each extruding a different substance onto the surface of the web such that multiple layers of additive are built onto the web, wherein different layers comprise different additive compositions.
  • the web 21 may pass through a boundary air blocking device 3 prior to reaching the meltblown die 27 .
  • a boundary air blocking device may be, for example, a stationary blocking device or a rotary blocking device which may deflect the flow of boundary air which may travel with the web and may carry lint and fiber which may clog the meltblown die tips.
  • the composition may be applied to the web 21 by use of meltblown die 27 .
  • meltblown die 27 In the embodiment wherein a meltblown die is used to extrude the composition onto the surface of the web, it has been discovered that the distance between the die tips and the web surface may be important not only for obtaining the desired coating pattern, but also for keeping lint and dust away from the die tips in order to prevent blockage of the composition flow.
  • the die tips may be between about 0.5 inch and about 3 inches from the web surface 45 as the composition is applied to the web. In one embodiment, the die tips may be between about 1 inch and about 2 inches from the surface of the web during the application process.
  • the system of the present invention may also include a vacuum box 7 .
  • the vacuum box 7 is provided to improve air flow and to employ a pneumatic force to pull the composition stream 29 down on to the first side 45 of the tissue web 21 .
  • FIG. 6 shows a top view of the vacuum box 7 as it would appear looking down from the meltblown die 27 (as shown in FIG. 5 ).
  • the vacuum box 7 includes multiple air intakes 48 (several of which are shown in FIG. 6 ).
  • the air intakes 48 are provided in a number of offset rows.
  • the air intakes 48 could be laid out with a different geometry, for instance a single row or even a series of channels to provide an air flow pulling the composition stream 29 from meltblown die 27 to the surface 45 of the web 21 .
  • a combination of channels and air intakes 48 could be used. There is no limit to the patterns that could be provided to the air intakes 48 of the vacuum box 7 for providing the desired air flow.
  • multiple air intakes 48 are in the top of the vacuum box 7 in offset rows which are at an angle ⁇ to the machine direction of the system.
  • the rows may be at an angle ⁇ of between about 5° and about 30°.
  • the rows of air intakes 48 may be set at an angle from the machine direction of about 15°.
  • Air intakes 48 may have a diameter which may depend, among other factors, on the web speed of the system. For example, at a web speed of between about 1,000 and about 3,000 feet/minute air intakes 48 may have a diameter of between about 1 ⁇ 4 inch and about 1 inch. In one embodiment, air intakes 48 may have a diameter of between about one-half inch and about five-eighths of an inch.
  • suitable vacuum pressure may be placed on the web when the angled rows of air intakes 48 comprise between about 3 and about 30 individual intakes per row of 10-inch width. In one embodiment, the rows may comprise between about 6 and about 15 individual air intakes per row of 20-inch width. For instance, a single row may include 10 individual air intakes 48 .
  • the web may be guided around a roll 11 to be properly aligned for application of the composition to the second surface 46 of the web 21 .
  • the surface 45 which now carries fibers of the composition 29 will contact the roll 11 .
  • Some of the composition may stick to the roll 11 as the web 21 is guided around roll 11 .
  • roll 11 may be cleaned with a roll cleaner 9 .
  • a roll cleaner such as an oscillating brush, a doctor blade, or a vacuum device may be used to prevent build up of composition 29 on guide roll 11 .
  • the second side or surface 46 of web 21 may then be applied with the same or a different polysiloxane composition in a process similar to that used to apply the composition 29 to the first surface 45 of the web 21 .
  • the second surface of the web 46 may have excess lint and fibers removed at sheet cleaner 1 before having the composition 29 applied to the surface 46 of the web 21 with meltblown die 27 .
  • the melt blown die tips may be protected from blockage due to lint and fibers carried in the air boundary with air boundary blocking device 3 .
  • Vacuum box 7 may provide desired air flow and help direct the deposit of the composition fibers on the surface 46 of the web 21 .
  • the sheet cleaner 1 and the boundary air blocking device 3 are intended to protect the orifices of the meltblown die 27 from buildup of lint and loose fibers.
  • the system of the present invention can include some type of cleaning device for actively cleaning the extruder or chemical additive applicator at selected times.
  • one embodiment of a cleaning device is shown in FIG. 7 .
  • the cleaning device includes a brush 60 that traverses across the die tip 28 of the extruder 27 .
  • the brush 60 includes a plurality of bristles that are intended to clean the orifices present on the extruder 27 .
  • the brush 60 is mounted on a track 62 which can be, for instance, a rodless air cylinder.
  • a rodless air cylinder for instance, the track 62 may be in communication with an air source 64 .
  • any suitable mechanism or device may be used in order to traverse the brush 60 across the extruder 27 .
  • pulleys, belts or chains may also be used.
  • the bristles contained on the brush 60 may be made from any suitable material.
  • the bristles can be made, for instance, from nylon or wool.
  • the brush 60 By periodically traversing across the die tip 28 of the extruder 27 , the brush 60 cleans the orifices through which the chemical additive is emitted.
  • the brush may remove lint, fibers and other debris that may accumulate and tend to block or clog the orifices.
  • FIG. 8 another embodiment of a cleaning device made in accordance with the present invention is shown.
  • the cleaning device is substantially similar to the cleaning device shown in FIG. 7 .
  • a shield member 64 is shown encircling or covering a substantial portion of the extruder 27 .
  • the shield member 64 prevents dust and debris from accumulating and building up in the crevices and other irregular structures that may exist on the extruder 27 .
  • the present inventors have discovered that the shield member creates a different dust buildup distribution pattern. Of particular advantage, the shield member keeps a significant portion of the dust and debris away from the orifices.
  • the shield member 64 further serves as a smooth running surface for the brush 60 .
  • the cleaning device further includes a scraping device 66 which is located within the path of travel of the brush 60 but outside the field of view of the die tip 28 of the extruder 27 .
  • the scraping device 66 is intended to clean the bristles of the brush 60 when the brush is traversed across the scraping device.
  • the scraping device 66 includes a flat edge that contacts the bristles and removes debris.
  • the system of the present invention can also include other means for cleaning the brush 60 .
  • a cleaning solvent may be applied to the brush 60 at selected times for further facilitating removal of debris and any chemical additive that may have transferred to the bristles of the brush.
  • the cleaning solvent may not only be used to clean the brush, but can also be used for cleaning the die head itself.
  • a cleaning solvent may be chosen that is well suited to removing any residual chemical additive present on the die head.
  • the cleaning solvent may be applied to the brush and/or to the die head using any suitable method.
  • the cleaning solvent may be applied to the die head and/or the brush using, for instance, a spray device.
  • the brush may be contacted with some type of cleaning fluid reservoir, such as a sponge, that transfers the cleaning fluid to the brush.
  • any suitable cleaning fluid may be used in the present invention.
  • the cleaning fluid chosen will depend upon the particular chemical additive being emitted by the extruder 27 .
  • cleaning fluids include aqueous solutions of detergents and organic solvents.
  • Particular organic solvents that may be used include ethanol, propanol, acetone, ethyl acetate, n-methyl pyrrolidinone, 2-pyrrolidinone, butyrolactone, tetrahydrofuran, 2-methoxyethyl ether, toluene, and the like.
  • FIG. 10 another embodiment of a cleaning device made in accordance with the present invention is shown.
  • the brush 60 rotates as it traverses across the extruder 27 .
  • the brush 60 includes bristles that extend around the entire circumference of the brush.
  • the brush is connected to a motor 68 that causes the brush to rotate.
  • the brush is shown rotating in a counterclockwise direction, it should be understood that the brush can also rotate in a clockwise direction.
  • the brush 60 extends substantially the entire length of the die tip 28 .
  • the brush instead of traversing across the die tip in a horizontal motion, the brush traverses across the die tip in a vertical motion.
  • the brush 60 includes a rotatable cylindrical core connected to a plurality of bristles that contact the die tip 28 .
  • the bristles may completely encircle the cylindrical core as shown in FIG. 11 .
  • the brush 60 may rotate continuously in a single direction, such as in a clockwise direction or in a counterclockwise direction.
  • the brush 60 when the brush 60 is not cleaning the orifices of the extruder 27 , the brush may be moved or otherwise pivoted from a cleaning position to a disengagement position. In the disengagement position, the brush is moved or otherwise pivoted outside the field of view of the die tip 28 .
  • the brush 60 may still move in a horizontal motion depending upon the motor used and the mechanical linkage configured between the brush and the motor.
  • the brush may be somewhat shorter than the width of the die tip 28 .
  • the brush may have a width that is about 80% of the width of the die tip. It should be understood, however, that in this embodiment the brush may have the same length as the die tip or may even be longer.
  • the system of the present invention may also use fluid nozzles or a vacuum source in order to clean the orifices of the extruder 27 .
  • the die tip 28 of the extruder 27 is shown positioned adjacent to a plurality of fluid jet nozzles 72 .
  • the fluid jet nozzles 72 are positioned across a common conduit 70 that is in turn connected to a pressurized fluid source.
  • the conduit can be, for instance, a pipe having a diameter of about 1′′ or less.
  • the fluid that is emitted from the nozzles 72 may be either a liquid or a gas.
  • the liquid may be, for instance, water or a cleaning solution.
  • a high pressure gas such as air, may be emitted from the nozzles 72 for cleaning the orifices of the die tip 28 .
  • the nozzles 72 may be used in addition to the brush 60 as shown in the previous figures.
  • FIG. 13 another embodiment of a cleaning device made in accordance with the present invention incorporating a plurality of fluid jet nozzles 72 is shown.
  • the fluid nozzles 72 may be independently controlled or, alternatively, may be connected to a common manifold.
  • the fluid nozzles 72 are mounted on a beam 74 connected to a linking structure 76 .
  • the linking structure allows the nozzles 72 to be rotated from an engagement position for cleaning the die tip 28 of the extruder 27 to a nonengagement position in which the nozzles are rotated out of the field of view of the orifices on the die tip.
  • the conduit 70 includes a single slit 78 instead of containing a plurality of nozzles 72 .
  • the slit 78 may be connected to a vacuum source for creating a suction force across the slit. In this manner, fibers, lint and debris may be sucked into the conduit 70 and collected in a filter instead of being blown off the die tip 28 .
  • individual suction chambers may also be connected to a vacuum source as described above.
  • fluid jet nozzles may be used in conjunction with a vacuum source for cleaning the die tip.
  • a brush 60 is shown that traverses across the die tip 28 of the meltblown die 27 .
  • the brush is placed in communication with a fluid channel 80 .
  • the brush may include at least one nozzle in communication with the fluid channel 80 .
  • the fluid channel 80 can then be used to deliver a flow of liquid or gas through the nozzles or can be used to deliver a suction force to the brush 60 .
  • the brush 60 may be used in conjunction with fluid jet nozzles and/or vacuum nozzles for assisting in cleaning the extruder 27 .
  • the extruder 27 may also be electrically grounded. Grounding the extruder and supporting equipment may neutralize charged surfaces on the chemical additive applicator and minimize the tendency of fibers, lint and other debris from collecting on the orifices contained on the extruder.
  • the flow rate of the composition through the die 27 may be, for instance, from about 2 grams/inch to about 9 grams/inch in one embodiment.
  • the flow rate will depend, however, on the composition being applied to the tissue web, on the speed of the moving tissue web, and on various other factors.
  • the total add on rate of the composition may be up to about 10% based upon the weight of the tissue web.
  • the polysiloxane softeners may be added to the web at a total add on rate of from about 0.05% to about 5% by weight of the tissue web.
  • a softener may be present in the tissue sheet in an amount of from about 0.1% to about 3% by weight.
  • the products of the present invention may also optionally include one or more beneficial agents.
  • the beneficial agents may be added to the web at a total add on rate of from about 0% to about 1% by weight of the tissue web.
  • the beneficial agents may be mixed together and/or with the softeners for combined application, or applied separately, as desired.
  • a single composition may be applied which comprises a combination of one or more polysiloxane softening agents and one or more beneficial agents.
  • a single composition may be prepared including a polysiloxane softener, Aloe Vera extract and Vitamin E.
  • the composition may be added to the web at an add on rate for the polysiloxane of between about 0.1% and about 1% by weight of the web, an add on rates for the Aloe of between about 0.01% and about 1% by weight of the web, and an add on rate for the vitamin E of between about 0.01% and about 1% by weight of the web.
  • a single composition may be applied which comprises from about 0% to about 30% by weight of the beneficial agents and from about 70% to about 100% by weight of one or more polysiloxane softeners.
  • the composition may include only the softeners and the beneficial agents, with no other additives.
  • the product web may have the polysiloxane softeners and the beneficial agents applied to the surface of the web in a variety of different layered arrangements and combinations.
  • all of the desired topical applications may be premixed and applied to the surface of the web at once, such that all of the fibrous additive on one side of the web is essentially the same and contains both the desired polysiloxanes and the desired beneficial agents.
  • the different agents may be applied in separate steps, creating layers of fibers on the surface of the web, each layer comprising different additives.
  • additives for example two different beneficial agents, may be pre-mixed and applied to the web surface together, while the other desired additives may be applied in one or more separate steps and form separate layers of fibers on the web either above or below the others, as desired. Any possible combination of additives is envisioned according to the present invention.
  • the composition may cover almost all or only a small portion of the surface area of the web depending upon the particular application. In general, the composition may cover from about 0.5% to about 99% of the surface area. In one embodiment, for example, the composition may cover from about 0.5% to about 5% of the surface area of the web. In an alternative embodiment, however, the composition may cover from about 20% to about 60% of the surface area of the web.
  • the viscosity of the composition may also vary depending upon the particular circumstances. When it is desired to produce fibers through the meltblown die, the viscosity of the composition should be relatively high. For instance, the viscosity of the composition may be at least 1000 cps, particularly greater than about 2000 cps, and more particularly greater than about 3000 cps. For example, the viscosity of the composition may be from about 1000 to over 100,000 cps, such as from about 1000 cps to about 50,000 cps and particularly from about 2000 to about 10,000 cps.
  • air pressure or air curtain 30 a - b on either side of the composition stream 29 is to assist in the formation of fibers, to attenuate the fibers, and to direct the fibers onto the tissue web.
  • Various air pressures may be used.
  • the temperature of the composition as it is applied to a tissue web in accordance with the present invention may vary depending upon the particular application. For instance, in some applications, the composition may be applied at ambient temperatures. In other applications, however, the composition may be heated prior to or during extrusion. The composition may be heated, for instance, in order to adjust the viscosity of the composition. The composition may be heated by a pre-heater prior to entering the meltblown die or, alternatively, may be heated within the meltblown die itself using, for instance, an electrical resistance heater.
  • the composition containing the chemical additive may be a solid at ambient temperatures (from about 20° C. to about 23° C.).
  • the composition may be heated an amount sufficient to create a flowable liquid that may be extruded through the meltblown die.
  • the composition may be heated an amount sufficient to allow the composition to be extruded through the meltblown die and form fibers. Once formed, the fibers are then applied to a web in accordance with the present invention.
  • the composition may resolidify upon cooling.
  • Other compositions that may need to be heated include compositions that contain a wax, that contain any type of polymer that is a solid at ambient temperatures, and/or that contain a silicone.
  • the process of the present invention may be used to apply compositions and chemical additives to numerous and various different types of products. For most applications, however, the present invention is directed to applying chemical additives to tissue products, particularly wiping products. While the current invention is applicable to any paper sheet, the process of the present invention is particularly well suited for use in conjunction with tissue and towel products. Tissue and towel products as used herein are differentiated from other paper products in terms of their bulk. The bulk of the products of this invention is calculated as the quotient of the caliper expressed in microns, divided by the basis weight, expressed in grams per square meter. The resulting bulk is expressed as cubic centimeters per gram.
  • tissue products of the present invention have a bulk greater than 2 cc/g, more preferably greater than 2.5 cc/g and still more preferably greater than about 3 cc/g.
  • one advantage of the present invention is the ability to apply viscous compositions, particularly polysiloxane compositions, without the need for water based diluents or application of Z-directional compression forces to the web during application of the chemical additive. Whenever water or Z-directional compressive forces are applied to the web the bulk of the web can be substantially reduced. As this invention avoids the need for water and Z-directional compressive forces it is particularly applicable to high bulk tissue products.
  • the final tissue product has a bulk of greater than about 7 cc/g, in another embodiment the final tissue product has a bulk of greater than about 8 cc/g and in still another embodiment the final tissue product has a bulk of greater than about 9 cc/g.
  • tissue sheets that are pattern densified or imprinted, such as the webs disclosed in any of the following U.S. Patents: U.S. Pat. No. 4,514,345, issued on Apr. 30, 1985 to Johnson et al.; U.S. Pat. No. 4,528,239, issued on Jul. 9, 1985 to Trokhan; U.S. Pat. No. 5,098,522, issued on Mar. 24, 1992; U.S. Pat. No. 5,260,171, issued on Nov.
  • Such imprinted tissue webs may have a network of densified regions that have been imprinted against a drum dryer by an imprinting fabric, and regions that are relatively less densified (e.g., “domes” in the tissue sheet) corresponding to deflection conduits in the imprinting fabric, wherein the tissue sheet superposed over the deflection conduits is deflected by an air pressure differential across the deflection conduit to form a lower-density pillow-like region or dome in the tissue sheet.
  • regions that are relatively less densified e.g., “domes” in the tissue sheet
  • drying operations may be useful in the manufacture of the tissue products of the present invention.
  • drying methods include, but are not limited to, drum drying, through drying, steam drying such as superheated steam drying, displacement dewatering, Yankee drying, infrared drying, microwave drying, radiofrequency drying in general, and impulse drying, as disclosed in U.S. Pat. No. 5,353,521, issued on Oct. 11, 1994 to Orloff and U.S. Pat. No. 5,598,642, issued on Feb. 4, 1997 to Orloff et al., the disclosures of both which are herein incorporated by reference to the extent that they are non-contradictory herewith.
  • Other drying technologies may be used, such as methods employing differential gas pressure include the use of air presses as disclosed U.S. Pat. No.
  • the tissue product may contain a variety of fiber types both natural and synthetic.
  • the tissue product comprises hardwood and softwood fibers.
  • the overall ratio of hardwood pulp fibers to softwood pulp fibers within the tissue product, including individual tissue sheets making up the product may vary broadly.
  • the ratio of hardwood pulp fibers to softwood pulp fibers may range from about 9:1 to about 1:9, more specifically from about 9:1 to about 1:4, and most specifically from about 9:1 to about 1:1.
  • the hardwood pulp fibers and softwood pulp fibers may be blended prior to forming the tissue web thereby producing a homogenous distribution of hardwood pulp fibers and softwood pulp fibers in the z-direction of the tissue web.
  • the hardwood pulp fibers and softwood pulp fibers may be layered (stratified fiber furnish) so as to give a heterogeneous distribution of hardwood pulp fibers and softwood pulp fibers in the z-direction of the tissue web.
  • the hardwood pulp fibers may be located in at least one of the outer layers of the tissue product and/or tissue webs wherein at least one of the inner layers may comprise softwood pulp fibers.
  • the tissue product contains secondary or recycled fibers optionally containing virgin or synthetic fibers.
  • synthetic fibers may also be utilized in the present invention.
  • pulp fibers is understood to include synthetic fibers.
  • suitable polymers that may be used to form the synthetic fibers include, but are not limited to: polyolefins, such as, polyethylene, polypropylene, polybutylene, and the like; polyesters, such as polyethylene terephthalate, poly(glycolic acid) (PGA), poly(lactic acid) (PLA), poly( ⁇ -malic acid) (PMLA), poly( ⁇ -caprolactone) (PCL), poly( ⁇ -dioxanone) (PDS), poly(3-hydroxybutyrate) (PHB), and the like; and, polyamides, such as nylon and the like.
  • polyolefins such as, polyethylene, polypropylene, polybutylene, and the like
  • polyesters such as polyethylene terephthalate, poly(glycolic acid) (PGA), poly(lactic acid) (PLA), poly( ⁇ -malic acid) (PMLA), poly( ⁇
  • Synthetic or natural cellulosic polymers including but not limited to: cellulosic esters; cellulosic ethers; cellulosic nitrates; cellulosic acetates; cellulosic acetate butyrates; ethyl cellulose; regenerated celluloses, such as viscose, rayon, and the like; cotton; flax; hemp; and mixtures thereof may be used in the present invention.
  • the synthetic fibers may be located in one or all of the layers and sheets comprising the tissue product.
  • the basis weight of tissue products treated in accordance with the present invention can also vary depending upon the ultimate use for the product.
  • the basis weight can range from about 6 gsm to 200 gsm and greater.
  • the tissue product can have a basis weight of from about 6 gsm to about 80 gsm.
  • a chemical additive is applied to a tissue web in accordance with the present invention while preserving the wettability and absorbency characteristics of the web.
  • many chemical additives that may be applied to tissue products are hydrophobic and thus when applied to a bath tissue across the surface of the tissue may adversely interfere with the ability of the tissue to become wet and disperse when being disposed of after use.
  • hydrophobic compositions such as aminopolysiloxanes may be applied to tissue webs and other paper products without adversely interfering with the wettability of the web.
  • the hydrophobic composition is applied to the web in a discontinuous manner, such that the coverage of the composition is heterogeneous across the web surface.
  • the hydrophobic composition may be applied across the surface of the web yet be applied to contain various voids in the coverage for permitting the web to become wet when contacted with water.
  • the hydrophobic composition is applied to the web as fibers that overlap across the surface of the web but yet leave areas on the web that remain untreated. In other applications, however, it should be understood that the viscous composition may be extruded onto the web so as to cover the entire surface area.
  • tissue web 21 treated in accordance with the present invention is shown.
  • the tissue web is illustrated in a dark color to show the presence of fibers or filaments 50 appearing on the surface of the web.
  • the filaments 50 intersect at various points and are randomly dispersed over the surface of the web, yet form a continuous network across the surface of the web. It is believed that the filaments 50 form a network on the surface of the web that increases the strength, particularly the wet strength and the geometric mean tensile strength of the web.
  • Geometric mean tensile strength is the square root of the product of the machine direction tensile strength and the cross-machine direction tensile strength of the web.
  • Tensile strength may be measured using an instron tensile tester using a 3-inch jaw width (sample width), a jaw span of 2 inches (gauge length), and a crosshead speed of 25.4 centimeters per minute after maintaining the sample under TAPPI conditions for 4 hours before testing.
  • the product webs of the present invention may have a geometric mean tensile strength of between about 400 g per 3 inches and about 1,500 g per 3 inches.
  • the filaments 50 only cover a portion of the surface area of the web 21 .
  • the composition used to form the filaments may be applied to the web so as to cover from about 20% to about 80% of the surface of the web, and particularly from about 30% to about 60% of the surface area of the web. By leaving untreated areas on the web, the web remains easily wettable. In this manner, extremely hydrophobic materials may be applied to the web for improving the properties of the web while still permitting the web to become wet in an acceptable amount of time when contacted with water and maintain a high level of absorbency.
  • the Wet Out Time of tissue webs treated in accordance with the present invention may be about 180 seconds or less, and more specifically about 120 seconds or less.
  • tissue webs treated in accordance with the present invention may have a Wet Out Time of about 60 seconds or less, still more specifically about 10 seconds or less, still more specifically from about 4 to about 8 seconds.
  • “Wet Out time” is related to absorbency and is the time it takes for a given sample to completely wet out when placed in water. More specifically, the Wet Out Time is determined by cutting 20 sheets of the tissue sample into 2.5-inch squares. The number of sheets used in the test is independent of the number of plies per sheet of product. The 20 square sheets are stacked together and stapled at each corner to form a pad. The pad is held close to the surface of a constant temperature distilled water bath (23+/ ⁇ 2° C.), which is the appropriate size and depth to ensure the saturated specimen does not contact the bottom of the container and the top surface of the water at the same time, and dropped flat onto the water surface, staple points down. The time taken for the pad to become completely saturated, measured in seconds, is the Wet Out Time for the sample and represents the absorbent rate of the tissue. Increases in the Wet Out Time represent a decrease in the absorbent rate.
  • various additives may be added to the composition in order to adjust the viscosity of the composition.
  • a thickener may be applied to the composition in order to increase its viscosity.
  • any suitable thickener may be used in accordance with the present invention.
  • polyethylene oxide may be combined with the composition to increase the viscosity.
  • polyethylene oxide may be combined with a polysiloxane softener and a beneficial agent to adjust the viscosity of the composition to ensure that the composition will produce fibers when extruded through the meltblown die.
  • Optional chemical additives may also be added to the aqueous papermaking furnish or to the embryonic tissue sheet to impart additional benefits to the product and process and are not antagonistic to the intended benefits of the present invention.
  • the following materials are included as examples of additional chemicals that may be applied to the tissue sheet with the additives of the present invention.
  • the chemicals are included as examples and are not intended to limit the scope of the present invention. They may also be added simultaneously with the additives applied via the fiber deposition apparatus.
  • Charge promoters and control agents are commonly used in the papermaking process to control the zeta potential of the papermaking furnish in the wet end of the process. These species may be anionic or cationic, most usually cationic, and may be either naturally occurring materials such as alum or low molecular weight high charge density synthetic polymers typically of molecular weight of about 500,000 or less. Drainage and retention aids may also be added to the furnish to improve formation, drainage and fines retention. Included within the retention and drainage aids are microparticle systems containing high surface area, high anionic charge density materials.
  • wet and dry strength agents may also be applied to the tissue sheet.
  • wet strength agents refer to materials used to immobilize the bonds between fibers in the wet state.
  • the means by which fibers are held together in paper and tissue products involve hydrogen bonds and sometimes combinations of hydrogen bonds and covalent and/or ionic bonds.
  • the wet state usually will mean when the product is largely saturated with water or other aqueous solutions, but could also mean significant saturation with body fluids such as urine, blood, mucus, menses, runny bowel movement, lymph, and other body exudates.
  • any material that when added to a tissue sheet or sheet results in providing the tissue sheet with a mean wet geometric tensile strength:dry geometric tensile strength ratio in excess of about 0.1 will, for purposes of the present invention, be termed a wet strength agent.
  • these materials are termed either as permanent wet strength agents or as “temporary” wet strength agents.
  • the permanent wet strength agents will be defined as those resins which, when incorporated into paper or tissue products, will provide a paper or tissue product that retains more than 50% of its original wet strength after exposure to water for a period of at least five minutes.
  • Temporary wet strength agents are those which show about 50% or less than, of their original wet strength after being saturated with water for five minutes. Both classes of wet strength agents find application in the present invention.
  • the amount of wet strength agent added to the pulp fibers may be at least about 0.1 dry weight percent, more specifically about 0.2 dry weight percent or greater, and still more specifically from about 0.1 to about 3 dry weight percent, based on the dry weight of the fibers.
  • Permanent wet strength agents will typically provide a more or less long-term wet resilience to the structure of a tissue sheet.
  • the temporary wet strength agents will typically provide tissue sheet structures that had low density and high resilience, but would not provide a structure that had long-term resistance to exposure to water or body fluids.
  • the temporary wet strength agents may be cationic, nonionic or anionic.
  • Such compounds include PAREZTM 631 NC and PAREZ® 725 temporary wet strength resins that are cationic glyoxylated polyacrylamide available from Cytec Industries (West Paterson, N.J.). This and similar resins are described in U.S. Pat. No. 3,556,932, issued on Jan. 19, 1971 to Coscia et al. and U.S. Pat. No. 3,556,933, issued on Jan. 19, 1971 to Williams et al. Hercobond1366, manufactured by Hercules, Inc., located at Wilmington, Del., is another commercially available cationic glyoxylated polyacrylamide that may be used in accordance with the present invention.
  • temporary wet strength agents include dialdehyde starches such as Cobond® 1000 from National Starch and Chemical Company and other aldehyde containing polymers such as those described in U.S. Pat. No. 6,224,714 issued on May 1, 2001 to Schroeder et al.; U.S. Pat. No. 6,274,667 issued on Aug. 14, 2001 to Shannon et al.; U.S. Pat. No. 6,287,418 issued on Sep. 11, 2001 to Schroeder et al.; and, U.S. Pat. No. 6,365,667 issued on Apr. 2, 2002 to Shannon et al., the disclosures of which are herein incorporated by reference to the extend they are non-contradictory herewith.
  • Permanent wet strength agents comprising cationic oligomeric or polymeric resins can be used in the present invention.
  • Polyamide-polyamine-epichlorohydrin type resins such as KYMENE 557H sold by Hercules, Inc., located at Wilmington, Del., are the most widely used permanent wet-strength agents and are suitable for use in the present invention.
  • Such materials have been described in the following U.S. Pat. Nos.: U.S. Pat. No. 3,700,623 issued on Oct. 24, 1972 to Keim; U.S. Pat. No. 3,772,076 issued on Nov. 13, 1973 to Keim; U.S. Pat. No. 3,855,158 issued on Dec. 17, 1974 to Petrovich et al.; U.S. Pat.
  • cationic resins include polyethylenimine resins and aminoplast resins obtained by reaction of formaldehyde with melamine or urea. It is often advantageous to use both permanent and temporary wet strength resins in the manufacture of tissue products with such use being recognized as falling within the scope of the present invention.
  • Dry strength agents may also be applied to the tissue sheet without affecting the performance of the present invention.
  • Such materials used as dry strength agents are well known in the art and include but are not limited to modified starches and other polysaccharides such as cationic, amphoteric, and anionic starches and guar and locust bean gums, modified polyacrylamides, carboxymethylcellulose, sugars, polyvinyl alcohol, chitosan, and the like.
  • Such dry strength agents are typically added to a fiber slurry prior to tissue sheet formation or as part of the creping package.
  • exemplary compounds include the simple quaternary ammonium salts having the general formula (R 1′ ) 4-b N + (R 1′′ ) b X ⁇ wherein R 1 ′ is a C 1-6 alkyl group, R 1′′ is a C 14 -C 22 alkyl group, b is an integer from 1 to 3 and X ⁇ is any suitable counterion.
  • R 1′ is a C 1-6 alkyl group
  • R 1′′ is a C 14 -C 22 alkyl group
  • b is an integer from 1 to 3
  • X ⁇ is any suitable counterion.
  • Other similar compounds include the monoester, diester, monoamide and diamide derivatives of the simple quaternary ammonium salts.
  • Additional softening compositions include cationic oleyl imidazoline materials such as methyl-1-oleyl amidoethyl-2-oleyl imidazolinium methylsulfate commercially available as Mackernium DC-183 from McIntyre Ltd., located in University Park, Ill. and Prosoft TQ-1003 available from Hercules, Inc.
  • the present invention may be used in conjunction with any known materials and chemicals that are not antagonistic to its intended use.
  • materials and chemicals include, but are not limited to, odor control agents, such as odor absorbents, activated carbon fibers and particles, baby powder, baking soda, chelating agents, zeolites, perfumes or other odor-masking agents, cyclodextrin compounds, oxidizers, and the like.
  • odor control agents such as odor absorbents, activated carbon fibers and particles, baby powder, baking soda, chelating agents, zeolites, perfumes or other odor-masking agents, cyclodextrin compounds, oxidizers, and the like.
  • Superabsorbent particles, synthetic fibers, or films may also be employed. Additional options include cationic dies, optical brighteners, absorbency aids and the like.
  • tissue sheets of the present invention may be included in the tissue sheets of the present invention including lotions and other materials providing skin health benefits including but not limited to such things as aloe extract and tocopherols such as Vitamin E and the like.
  • the application point for such materials and chemicals is not particularly relevant to the present invention and such materials and chemicals may be applied at any point in the tissue manufacturing process. This includes pre-treatment of pulp, co-application in the wet end of the process, post treatment after drying but on the tissue machine and topical post treatment.
  • X-ray photoelectron spectroscopy is a method used to analyze certain elements lying on the surface of a material. Sampling depth is inherent to XPS. Although the x-rays can penetrate the sample microns, only those electrons that originate at the outer ten Angstroms below the solid surface can leave the sample without energy loss. It is these electrons that produce the peaks in XPS. The electrons that interact with the surrounding atoms as they escape the surface form the background signal.
  • the sampling depth is defined as 3 times the inelastic mean free path (the depth at which 95% of the photoemission takes place), and is estimated to be 50-100 angstroms. The mean free path is a function of the energy of the electrons and the material that they travel through.
  • the flux of photoelectrons that come off the sample, collected, and detected is elemental and instrumental dependent. It is not overly critical to the results as herein expressed.
  • the atomic sensitivity factors are various constants for each element that account for these variables.
  • the atomic sensitivity factors are supplied with the software from each XPS instrument manufacturer. Those skilled in the art will understand the need to use the set of atomic sensitivity factors designed for their instrument.
  • Ix peak intensity of photoelectron of element x
  • the relative surface concentration and z-directional gradient of chemical additives on tissue samples may be determined by x-ray photoelectron spectroscopy (XPS) using a Fisions M-Probe spectrometer equipped with monochromatic Al K ⁇ x-rays, as reported in Surface Interface Analysis, vol 10, pages 36-47 (1987).
  • XPS x-ray photoelectron spectroscopy
  • tissue sheets treated with a chemical additive are placed in a successive fashion to form a stack.
  • the stack of tissue sheets are wrapped in aluminum foil for storage prior to being analyzed.
  • Samples are prepared from a single sheet of material obtained from the center of the stack.
  • a center sheet is chosen to prevent the possibility of smearing of the treatment or cross-contamination with the packaging.
  • a ca. 1 cm ⁇ 1 cm representative section is cut from the center of a selected sheet.
  • the 1 cm ⁇ 1 cm section is divided in half.
  • the outer fibers are analyzed from one half and the opposite side is analyzed from the second half.
  • Each section of tissue is mounted to a sample holder using a silicone free double sided tape such as ScotchTM Brand Double Stick Tape.
  • the mounted samples are placed in the introduction chamber and allowed to pump down to at least 1 ⁇ 10 ⁇ 4 torr prior to moving them into the analyzing chamber. Prior to analysis, the base pressure in the analysis chamber is allowed to reach 1.0 ⁇ 10 ⁇ 7 torr or less.
  • a metal screen is placed over the samples and charge compensation is accomplished using an electron flood gun.
  • the flood gun is adjusted to optimize peak height and minimize the resolution of the C1s peak.
  • the same charging compensation is used for all the samples.
  • the binding energy scale of each spectra is adjusted by referencing the C—C/C—H contribution of the C1s peak to 285.0 eV.
  • Survey spectra from 0-600 eV are acquired from each sample. Three regions are analyzed per sample and the results averaged.
  • the polydimethylsiloxane content on cellulose fiber substrates is determined using the following procedure.
  • a sample containing polydimethylsiloxane is placed in a headspace vial, boron trifluoride reagent is added, and the vial sealed. After reacting for about fifteen minutes at about 100° C., the resulting Diflourodimethyl siloxane in the headspace of the vial is measured by gas chromatography with an FID detector.
  • the instrument is controlled by, and the data collected using, Perkin-Elmer Nelson Turbochrom software (version 4.1). An equivalent software program may be substituted.
  • the gas chromatograph is equipped with a Hewlett-Packard headspace autosampler, HP-7964 and set up at the following conditions:
  • the gas chromatograph is set to the following instrument conditions:
  • Carrier gas Helium
  • the method is calibrated to pure PDMS using DC-200 fluid available from Dow Corning, Midland, Mich.
  • the Calibration Standards are made to bracket the target concentration by adding 0 (blank), 50, 100, 250, and 500 ⁇ L of the Stock Solution (the volume in uL V c recorded) to successive 20 mL headspace vials containing 0.1 ⁇ 0.001 grams of an untreated control tissue web or tissue product.
  • the solvent is evaporated by placing the headspace vials in an oven at a temperature ranging between about 60° C. to about 70° C. for about 15 minutes.
  • tissue sample 0.100 ⁇ 0.001 g is weighed to the nearest 0.1 mg into a 20-ml headspace vial.
  • the sample weight (represented as W s ) in mg is recorded.
  • the amount of tissue web and/or tissue product taken for the standards and samples must be the same.
  • BF 3 reagent 100 ⁇ L of BF 3 reagent is added to each of the samples and calibration standards. Each vial is sealed immediately after adding the BF 3 reagent.
  • the sealed vials are placed in the headspace autosampler and analyzed using the conditions described previously, injecting 1 mL of the headspace gas from each tissue sample and standard.
  • a calibration curve of ⁇ g dimethylpolysiloxane versus analyte peak area is prepared.
  • the analyte peak area of the tissue sample is then compared to the calibration curve and amount of polydimethylsiloxane (represented as (A)) in ⁇ g on the tissue web and/or tissue product is determined.
  • Non-ionic surfactant concentration in a tissue can be determined using appropriate test kits and measuring the absorbency at a wavelength of 620 nm.
  • Non-ionic surfactant levels may be measured, for instance, using Dr. Lange non-ionic test solutions available from Dr. Bruno Lange, GmbH, Dusseldorf, Germany.
  • a Hach DR/2000 spectrometer or equivalent is used to measure the absorbance of the specimen. Water samples are prepared by repulping 30 grams of the tissue or fiber in 2 L of deionized water. Smaller sample sizes may be used, for example 3.0 grams of tissue can be slurried in 200 cc of deionized water. The fiber is filtered off using a Britt Jar filter and the filtrate is used as the water sample. The procedure is as follows:
  • a conventional polysiloxane formulation was applied to a through-dried tissue web using a rotogravure coater.
  • several different polysiloxane compositions were applied to the same bath tissue according to the present invention.
  • neat polysiloxane compositions were fiberized using a uniform fiber depositor marketed by ITW Dynatec and applied in a discontinuous fashion to the tissue web.
  • a single-ply, three-layered uncreped throughdried bath tissue was made using eucalyptus fibers for the outer layers and softwood fibers for the inner layer.
  • a quaternary ammonium softening agent (C-6027 from Goldschmidt Corp.) was added at a dosage of 4.1 kg/metric ton of active chemical per metric ton of fiber to the eucalyptus furnish.
  • the slurry was dewatered using a belt press to approximately 32% consistency.
  • the filtrate from the dewatering process was either sewered or used as pulper make-up water for subsequent fiber batches but not sent forward in the stock preparation or tissue making process.
  • the thickened pulp containing the debonder was subsequently re-dispersed in water and used as the outer layer furnishes in the tissue making process.
  • the softwood fibers were pulped for 30 minutes at 4 percent consistency and diluted to 3.2 percent consistency after pulping, while the debonded eucalyptus fibers were diluted to 2 percent consistency.
  • the overall layered sheet weight was split 30%/40%/30% among the eucalyptus/refined softwood/eucalyptus layers.
  • the center layer was refined to levels required to achieve target strength values, while the outer layers provided the surface softness and bulk. Parez 631NC was added to the center layer at 2-4 kilograms per ton of pulp based on the center layer.
  • a three layer headbox was used to form the web with the refined northern softwood kraft stock in the two center layers of the headbox to produce a single center layer for the three-layered product described.
  • Turbulence-generating inserts recessed about 3 inches (75 millimeters) from the slice and layer dividers extending about 1 inch (25.4 millimeters) beyond the slice were employed.
  • the net slice opening was about 0.9 inch (23 millimeters) and water flows in all four headbox layers were comparable.
  • the consistency of the stock fed to the headbox was about 0.09 weight percent.
  • the resulting three-layered sheet was formed on a twin-wire, suction form roll, former with forming fabrics being Lindsay 2164 and Asten 867a fabrics, respectively.
  • the speed of the forming fabrics was 11.9 meters per second.
  • the newly-formed web was then dewatered to a consistency of about 20-27 percent using vacuum suction from below the forming fabric before being transferred to the transfer fabric, which was traveling at 9.1 meters per second (30% rush transfer).
  • the transfer fabric was an Appleton Wire T807-1. A vacuum shoe pulling about 6-15 inches (150-380 millimeters) of mercury vacuum was used to transfer the web to the transfer fabric.
  • the web was then transferred to a throughdrying fabric (Lindsay wire T1205-1).
  • the throughdrying fabric was traveling at a speed of about 9.1 meters per second.
  • the web was carried over a Honeycomb throughdryer operating at a temperature of about 350° F., (175° C.) and dried to final dryness of about 94-98 percent consistency.
  • the resulting uncreped tissue sheet was then wound into a parent roll.
  • the parent roll was then unwound and the web was calendered twice.
  • the web was calendered between a steel roll and a rubber covered roll having a 4 P&J hardness.
  • the calender loading was about 90 pounds per linear inch (pli).
  • the web was calendered between a steel roll and a rubber covered roll having a 40 P&J hardness.
  • the calender loading was about 140 pli.
  • the thickness of the rubber covers was about 0.725 inch (1.84 centimeters).
  • the aqueous emulsion contained 25% polydimethylsiloxane (Wetsoft CTW of Kelmar Industries); 8.3% surfactant; 0.75% antifoamer and 0.5% preservative.
  • the gravure rolls were electronically engraved, chrome over copper rolls supplied by Specialty Systems, Inc., Louisville, Ky.
  • the rolls had a line screen of 200 cells per lineal inch and a volume of 6.0 Billion Cubic Microns (BCM) per square inch of roll surface. Typical cell dimensions for this roll were 140 microns in width and 33 microns in depth using a 130 degree engraving stylus.
  • the rubber backing offset applicator rolls were a 75 shore A durometer cast polyurethane supplied by Amerimay Roller company, Union Grove, Wis. The process was set up to a condition having 0.375 inch interference between the gravure rolls and the rubber backing rolls and 0.003 inch clearance between the facing rubber backing rolls.
  • the simultaneous offset/offset gravure printer was run at a speed of 2000 feet per minute using gravure roll speed adjustment (differential) to meter the polysiloxane emulsion to obtain the desired addition rate.
  • the gravure roll speed differential used for this example was 1000 feet per minute.
  • the process yielded an add-on level of 2.5 weight percent total add-on based on the weight of the tissue (1.25% each side).
  • UFD uniform fiber depositor
  • the uniform fiber depositor had 17 nozzles per inch and operated at an air pressure of 20 psi.
  • the die applied a fiberized neat polysiloxane composition onto the web.
  • the polysiloxanes used in this example included
  • EXP-2076 an alkoxy functional poly(dialkyl)siloxane of Kelmar Industries
  • the polysiloxanes were added to the web to yield an add-on level as shown in Table 1, below.
  • each web was tested for Wet Out Time and for geometric mean tensile strength (GMT) as described above.
  • GMT geometric mean tensile strength
  • the webs were tested for softness and stiffness values which were obtained through a Sensory Profile Panel testing method.
  • a group of 12 trained panelists were given a series of tissue prototypes, one sample at a time. For each sample, the panelists rate the tissue for softness and stiffness on a letter grade scale, with A being the highest ranking. Results are reported as an average of panel rankings. The following results were obtained:
  • tissue samples treated with the uniform fiber deposition method generally had a shorter wet out time with a stronger geometric mean tensile strength and excellent stiffness and softness characteristics.
  • the atomic % silicone is measured at five places on the exterior surface of the single ply treated tissue of Sample No. 2 and the average found to be about 20 atom % on the exterior surface.
  • a tape split is made of the material and the atom % silicone on the interior surface measured at five places using XPS.
  • the atom % silicone is found to be 15% for a delta % between the center and exterior surface of 25%.
  • the atomic % silicone is measured at five places on the exterior surface of the treated tissue of the control.
  • the average atom % silicone is found to be about 18%.
  • a tape split is made and the % silicone on the interior surface measured at five places using XPS spectroscopy.
  • the average atom % silicone is determined to be 17% for a delta % between the center and the exterior surface of 5%.
  • a multi-ply commercially available polysiloxane treated facial tissue that has been treated on only one side of the exterior plies is taken and the atom % silicone on the outside treated surface is determined to be 20.9 atom %.
  • the interior non-treated side of the treated ply is then measured and determined to have a surface silicone concentration of 18.8 atom %. Assuming an even gradient of polysiloxane in the z-direction the delta % between the center and exterior surface of the treated ply is 5.6%.
  • This particular sample is prepared using a gravure printing process.
  • Another commercially available multi-ply silicone treated facial tissue that has been treated on only one side of the exterior plies is taken and the atom % silicone on the outside treated surface determined to be 10.3 Atom %.
  • the interior non-treated side of the treated ply is then measured and determined to have a surface silicone concentration of 8.7 atom %. Assuming an even gradient of polysiloxane in the z-direction the delta % between the center and exterior surface of the treated ply is 7.3%.
  • This particular sample is believed to have been prepared using a process similar to that of the previous commercially available tissue.

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US10/441,143 US7396593B2 (en) 2003-05-19 2003-05-19 Single ply tissue products surface treated with a softening agent
EP20040717506 EP1627108B1 (fr) 2003-05-19 2004-03-04 Produits en papier tissu monocouche traites en surface avec un adoucisseur
KR1020057020915A KR20060008978A (ko) 2003-05-19 2004-03-04 연화제로 표면 처리된 한겹 티슈 제품
BRPI0410008 BRPI0410008A (pt) 2003-05-19 2004-03-04 folha de papel tecido de dobra única ou múltipla e aparelho para aplicação de aditivos quìmicos a tramas fibrosas
AU2004242060A AU2004242060B2 (en) 2003-05-19 2004-03-04 Single ply tissue products surface treated with a softening agent
CA2524685A CA2524685C (fr) 2003-05-19 2004-03-04 Produits en papier tissu monocouche traites en surface avec un adoucisseur
PCT/US2004/006913 WO2004104298A2 (fr) 2003-05-19 2004-03-04 Produits en papier tissu monocouche traites en surface avec un adoucisseur
MXPA05011736A MXPA05011736A (es) 2003-05-19 2004-03-04 Productos de tisu de estrato unico tratados de superficie con un agente suavizador.
EP20080005963 EP1950346A3 (fr) 2003-05-19 2004-03-04 Surface de produits de tissu à simple pli traitée avec un agent adoucissant
US12/165,152 US7897015B2 (en) 2003-05-19 2008-06-30 Single ply tissue products surface treated with a softening agent

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CA2524685C (fr) 2012-01-17
AU2004242060B2 (en) 2009-03-12
EP1950346A2 (fr) 2008-07-30
EP1627108A2 (fr) 2006-02-22
BRPI0410008A (pt) 2006-04-25
EP1950346A3 (fr) 2011-01-26
US7897015B2 (en) 2011-03-01
WO2004104298A3 (fr) 2005-09-09
EP1627108B1 (fr) 2013-07-17
CA2524685A1 (fr) 2004-12-02
US20080257512A1 (en) 2008-10-23
MXPA05011736A (es) 2006-01-26

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